An Organocopper(III) Fluoride Triggering C−CF3 Bond Formation

Author:

Joven‐Sancho Daniel1ORCID,Echeverri Andrea2ORCID,Saffon‐Merceron Nathalie3ORCID,Contreras‐García Julia2ORCID,Nebra Noel1ORCID

Affiliation:

1. Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA) Université Paul Sabatier, CNRS 118 Route de Narbonne 31062 Toulouse France

2. Laboratoire de Chimie Théorique (LCT) Sorbonne Université, CNRS 4, Place Jussieu 75005 Paris France

3. Institut de Chimie de Toulouse ICT-UAR2599 Université Paul Sabatier, CNRS 31062 Toulouse Cedex France

Abstract

AbstractCopper(III) fluorides are catalytically competent, yet elusive, intermediates in cross‐coupling. The synthesis of [PPh4][CuIII(CF3)3F] (2), the first stable (isolable) CuIII−F, was accomplished via chloride addition to [CuIII(CF3)3(py)] (1) yielding [PPh4][CuIII(CF3)3Cl(py)] (1⋅Cl), followed by treatment with AgF. The CuIII halides 1⋅Cl and 2 were fully characterized using nuclear magnetic resonance (NMR) spectroscopy, single crystal X‐ray diffraction (Sc‐XRD) and elemental analysis (EA). Complex 2 proved capable of forging C−CF3 bonds from silyl‐capped alkynes. In‐depth mechanistic studies combining probes, theoretical calculations, trapping of intermediate 4a ([PPh4][CuIII(CF3)3(C≡CPh)]) and radical tests unveil the key role of the CuIII acetylides that undergo facile 2e reductive elimination furnishing the trifluoromethylated alkynes (RC≡CCF3), which are industrially relevant synthons in drug discovery, pharma and agrochemistry.

Funder

Agence Française de Sécurité Sanitaire de l'Environnement et du Travail

Publisher

Wiley

Subject

General Chemistry,Catalysis

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